JP2001521968A - Improved extensible resin composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to a dispersion of fibrids and a method of using the dispersion in a resin composition to increase the extensibility of a cured film made from the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to highly improved extensible resin compositions and methods of achieving this improved extensibility.

BACKGROUND ART In general, aqueous resin compositions such as paints, coatings, sealers, and corks (cau)
lks) and fillers improve elongation by adding plasticizers to the composition or by altering the properties of the resin itself, for example, by lowering the glass transition temperature (Tg) of the resin. Such modifications have the potential to significantly affect the overall performance of the resin composition.

[0003] Fibers and fillers have been used in the past to fortify resin compositions. However, while reinforcing materials improve tensile strength and modulus, they reduce the extensibility of the composition.

[0004] Examples of the teachings of reinforced resin compositions include US Pat. No. 4,514,541, which teaches the reinforcement of elastomers by incorporating short p-aramid fibers into the elastomer composition, the use of fibrids for reinforcement of elastomers. No. 5,331,053 teaching the use, and US Pat. No. 4,460,737 teaching the use of polyolefin fibers in polyurethane sealers.

[0005] The present invention relates to the use of special organic polymeric materials in resin compositions. The polymeric material is fibrids. Fibrids are not fibers.
Fibrids are organic particulates that are film-like and have a medium to relatively high surface area. The fibrids allow the polymer solution to be stirred while vigorously stirring the coagulation bath.
It is made by extruding or spinning a non-solvent (relative to the polymer) into the bath. However, this non-solvent needs to be mixed with the solvent of the polymer solution.

[0006] Fibrids were first introduced in US Patent No. 2,999,788 to Morgan. Morgan teaches how to make fibrids and their various uses. However, unlike the present invention, Morgan does not teach fibrid dispersions, ie, combinations of fibrids and fillers in aqueous dispersions. Morgan suggests the use of fibrids as a material for the reinforcement of resins and resin compositions, but does not teach how to use fibrids as a means of improving the extensibility of resin compositions.

The present invention provides an aqueous dispersion of fibrids stabilized in water by a combination of an inorganic particulate filler, a coupling agent and a surfactant. Then, this dispersion can be mixed with the resin composition to form a mixture. Cured films made from this mixture exhibit 2-3 times the extensibility of cured films made from the resin composition alone. At the same time, the strength of the cured film made from this mixture is about the same as the cured film made from the resin composition alone.

[0008] It is an object of the present invention to provide a cured film that exhibits high extensibility and high elastic behavior. It is another object of the present invention to provide flexibility in the formulation of the resin composition so that comparable extensibility can be achieved using hard or inexpensive components.

BRIEF DESCRIPTION OF THE INVENTION The present invention comprises at most 0.5% by weight of fibrids, at most 5% by weight of inorganic particulate fillers and coupling agents and surfactants, provided that the cup It is to provide an aqueous dispersion, manufactured and stabilized under high shear, in which the ringing agent and the surfactant are present in a concentration sufficient to maintain the fibrids and the inorganic filler in the dispersion.

[0010] A second aspect of the present invention is given when this aqueous dispersion is mixed into a resin composition. Thus, the present invention relates to a coupling in which at most 0.5% by weight of fibrids and at most 5% by weight of inorganic particulate filler are each present in a concentration sufficient to maintain the fibrids and the inorganic filler in the dispersion. Mixing the aqueous dispersion comprising the agent with the surfactant together with the surfactant into the composition, provided that the concentration of the aqueous dispersion in the resin composition increases the fibrid concentration in the resin composition by at most about 0.1%. Provided is an improved resin composition comprising water or an affinity for water, comprising a dispersed resin and additives, at a concentration of 25%. The cured film made from the improved resin composition is a cured film made of a resin composition not containing the fibrid dispersion.
-Shows 3 times improved extensibility.

The resin composition containing the fibrid dispersion of the present invention can be used for producing paints, sealers, coke, filling compounds and the like.

DETAILED DESCRIPTION OF THE INVENTION Additives as used herein refer to substances other than the resins or solvents typically used in resin compositions. Additives include pigments, extenders, fillers, thickeners,
Dispersing aids include surfactants, dispersants, coupling agents, and pH buffering chemicals.

[0013] Fibrid as used herein refers to film-like polymer particles. By film-like is meant that the fibrids have two relatively large dimensions, length and width, and a thickness of very small dimensions. Generally fibrids fibrids about 50 with a surface area of 300m ² / g, 10-10 00 microns in length, i.e., has a maximum length, the preferred maximum dimension 10-200
Micron. The smallest dimension, i.e., thickness, is from about 0.05 to about 0.25 microns. Generally, these dimensions are for individual fibrids, but the dimensions also characterize the fibrid mass. Fibrids can be formulated from a variety of polymeric materials. No. 5,209,877, U.S. Pat. No. 3,756,908, U.S. Pat.
No. 018091, or U.S. Pat. No. 2,999,788. Generally, fibrids are made by spinning (coagulating) a polymer solution in a non-solvent for the polymer with vigorous stirring of a coagulation bath. M-aramid fibrids are available from E. coli. I. It is commercially available from DuPont (Wilmington, DE). DuPont fibrids are sold completely dry or dry. Either form can be used in the present invention, but non-dried fibrids are preferred.

Attempts have been made to incorporate fibrids into thin films, but relatively large
The presence of fibrids in the film gave a gloss that was too low and a film that was too coarse. These early experiments simply mixed fibrids with other additives and fillers into the resin composition and did not perform any special formulation or pre-dispersion of fibrids.

[0015] The fibrid dispersion of the present invention can be prepared using various solvents or solvent mixtures. The solvent (s) used to make the dispersion will depend on the solvent and resin of the resin composition incorporating the fibrid dispersion. Fibrids, as shown below, are commercially available as dry particles or dispersed in water. Fibrids can also be made from a variety of polymers, as described below, and can solidify in liquids to have a wide range of properties. That is, the fibrids and the liquid as a carrier associated with the fibrids can be selected to suit the desired use.

A preferred liquid for the fibrid dispersion of the present invention is water. For these suitable fibrid dispersions, a resin composition as used herein is an aqueous composition or a composition that is compatible with the aqueous fibrid dispersion. This affinity means that the resin composition and the fibrid dispersion are mixed together without separation into layers or separation of components from the composition or without coagulation of the composition. Resin compositions include paints, coatings, sealer compositions, coke, and the like. Generally, these are latex compositions in which water is present as at least a portion of the composition solvent system.

The fibrid dispersion of the present invention needs to disperse the fibrids under relatively high shear in the presence of inorganic particulate matter, a coupling agent and a surfactant. The fibrid dispersion contains fibrids at a concentration of 0.5% by weight or less of the dispersion. The concentration of the inorganic particulate matter is at most about 5% by weight. Most preferred concentrations have a fibrid concentration of at most about 0.4% and an inorganic particulate matter concentration of about 2-4%. In this concentration range, the fibrid dispersion has a water-like viscosity.

[0018] Coupling agents are small molecules that assist in the dispersion of solid particulate matter in a liquid medium and are of the following types: silanes, titanates and zirconates. Surfactants are large molecules that have different functionalities in the molecule and thus aid in the dispersion of solid particulate matter in liquid media. Surfactants can be anionic, nonionic or cationic. The type and concentration of the surfactant and the coupling agent depend on the nature of the granules to be dispersed and the nature of the liquid in which the particles are dispersed. Coupling agents useful in the present invention include Silk Quest (S) manufactured by Witco Corp.
ILQUEST) brand products, A-1106, A-87 and A-100; Kr55 from Ken-React, Lica 38 and K-Leica 97-WE50, titanate and NZ from Ken-React. −01, N
Z-97, including zirconate. A suitable coupling agent is Leica 97-WE5
0, Silk Quest A-187 and A-1100. For aramid fibrids, Silk Quest A-1100 is most preferred.

Surfactants useful in the present invention are non-ionic compounds, such as PLURONIC products P-103 and P-105 from BASF and Iconol (I
CONOL) DA-6-90, Akzo Nobell Chemicals (Akzo Nob)
El Chemicals' products AROMOX DM-16, Byk Chemie's ETHOMID products 0 /
17 and HT-23, DISPERBYK 181, 3M FC-430, Union Carbide TRITON products X-14 and X-705, and Air Products (A
surf products (SURFYNOL) CT-11
1; anionic compounds such as Dispervik 110 and Vic products 156 and 151 from Bik Hemy, FC-129 from 3M, and Surfynol CT-131 from Air Products, and cationic compounds such as Vic -Includes Dispervic 130 and 182 from Hemy and FC-135 from 3M. Surfactants suitable for the present invention are FC-430, Dispervik 181 and Aromox DM
-16, with Aromox DM-16 being the most preferred.

The concentrations of the coupling agent and the surfactant are generally lower than the other components of the resin composition, but each of them must be used in an amount sufficient to stabilize the fibrid dispersion. . The amounts of each of these components for use in the fibrid composition or in the total resin composition can be determined by subjecting the dispersion to a given concentration of coupling agent and surfactant and determining the degree of grind in ASTM Test 1210. Can be determined experimentally by checking In this test, the dispersion or composition is ground (evaporated) on a grind or Hegman gauge to determine at which film thickness the granules protrude above the surface of the film. The concentration of the coupling agent and / or surfactant can be adjusted to produce the thinnest film capable of a smooth dispersion without the presence of particulate matter.

The inorganic particulate used in the present invention may be a substance known as a filler, a pigment, or an extrudate. These materials include clay, calcium carbonate, talc, silica, titanium dioxide, mica, silicates, glasses, oxides, and the like. These particulates can be selected from inorganic materials that are already part of the resin composition and should be selected so as to be miscible with the resin composition and that the composition meets the desired performance criteria. For example, inorganic particulate matter is available in various particulate sizes and with various surface treatments. The criteria needed are that the inorganic material provide a harder surface than the fibrid mass intended to aid dispersion, and that these particles be included in the final formulation of the improved resin composition having the desired properties. The particles must have appropriate particle size and thixotropy. For example, if the particulate clay is part of the original resin composition, it is used in the fibrid dispersion as long as the clay disperses and stabilizes the fibrid at a concentration of 5% by weight or less in the fibrid dispersion. You may consider that. Regarding the selection and concentration of the coupling agent and the surfactant, a grind gauge can be used to assist in the selection of the inorganic particles used in the present invention. Particularly suitable inorganic particulates are abrasive filler clays, such as Florid (Fluor), for relatively low cost reasons.
MINUGEL manufactured by Idin Co., Ltd. If desired, pigments that match the formulation and expected color of the final resin composition can be used.

To achieve the fibrid dispersions of the present invention, it is necessary to mix the components together under high shear. Dispersion methods known in the art of coating production that provide high shear can be used to prepare the fibrid dispersions of the present invention. For example, about 5000-100
A Cowles blade disperser or emulsifier at 00 rpm provides adequate shear to disperse the fibrids. The time required is about 30 to about 9
0 minutes. Heating reduces the time required to make the dispersion. This heating may be by an external source, but is usually sufficient to heat the mixture at a shear rate. Cooling is usually required to regulate the temperature to a certain value. Preferably, the fibrid dispersion is made in an emulsifier at about 230 ° F (110 ° C) for about 1 hour. Again, a grind gauge may be used to check the fibrid dispersion and determine the grinding conditions (temperature, time, shear rate) for the dispersion. These conditions are the inorganic particulates used to produce the fibrid dispersion,
It can be changed depending on the selection of the surfactant and the coupling agent. The order of addition of the ingredients to the grind vessel is not critical.

Once the fibrid dispersion has been made, it can be incorporated into the resin composition with low shear, for example by mixing with stirring.

Preferred fibrid dispersion concentrations are those that give a total fibrid concentration of about 0.15% by weight in the mixture of resin composition and dispersion. At this total fibrid content concentration, the viscosity of the resin mixture does not increase due to the fibrids present, but may increase due to the presence of inorganic particulates present in the fibrid dispersion. In practice, it is recommended to reduce the thickener or possibly other viscosity-enhancing component content of the resin composition, so that the addition of inorganic particulates is acceptable and generally does not alter the properties of the improved resin composition. Is done. The formulation of the resin composition will vary depending on the expected properties of the composition and the end use. However, the addition of fibrids by the fibrid dispersion of the present invention can be carried out such that all properties are hardly changed as compared with the control (resin composition to which no fibrid dispersion is added). More importantly, the addition of the fibrid dispersion allows flexibility in the formulation of the resin composition. For example, as the elongation of the mixture increases, tougher, less plasticizer, and higher Tg resins can be used. With the addition of inorganic particulates that are part of the fibrid dispersion, the amount of cellulose or other thickener in the formulation can be reduced. Eliminating or reducing the cellulose content of the formulation increases the sensitivity of the formulation to water. This feature of the present invention is particularly useful in outdoor applications, such as resin compositions used in sealers, coke, fill compounds, or outdoor paints, coatings, and finishes.

The present invention provides an aqueous dispersion that can be used to improve the extensibility of a resin composition or a composite. Such composites include paints, sealers, coke, filler compounds and adhesives. The composition is improved by incorporating a fibrid dispersion into the composition. A suitable amount of fibrid dispersion to be incorporated into such a resin composition is such that the weight percent of fibrids in the composition is less than or equal to about 0.25%, preferably 0.15%. Test Method Viscosity was measured with a Brookfield viscometer. Measurements were taken at 72 ° F. (22 ° C.) and after manually stirring the sample for 1 minute.

The anti-sag is ASTM D4400, leveling (le
level was measured according to ASTM D4062 and adhesion was measured according to ASTM D3359.

Texture and gloss were visually observed on a scale of 0-10. In the case of texture, a report of 0 indicates a smooth surface, while a value of 10 indicates a very rough surface. In the case of gloss, a report of 0 indicates no gloss and a reading of 10 indicates that the film has a certain shine.

[0028] Tensile and extensibility were measured on cured, dry, free films using Instron Model 1000 at a speed of 5 inches / minute. This free film was prepared by drawing down 10 mils on an E-coated metal panel that had been treated to allow easy release of the film. The film was cured at 120 ° F. (49 ° C.) for 24 hours, peeled from the panel and cut into strips of the shape required for testing. The tensile strength and elongation of the cut strip were measured. EXAMPLES The following examples illustrate the invention but are not intended to limit it. Example 1 This example illustrates the preparation of a fibrid dispersion of the present invention and the use of this dispersion in outdoor acrylic paint formulations.

The dispersion is a Ross mixer emulsifier ME-100L having a fine sieve head.
Manufactured using Form C.

The following materials were placed in a quartz can: 466.2 g of distilled water, 7.5 g of A-1100 silane, Fibrid F-20W from DuPont (92% moisture) (not dried)
28.2 g and Minugel PC clay 25.5 g. 7000 rpm
For 30 minutes. Stop the Ross mixer and turn on Colloid 643
Was added to the mixture. The loss mixer was started again and mixed for another 2 hours at 7000 rpm. Water was then added to make up the water evaporated during the mixing operation. The fibrids were well dispersed. This dispersion is the dispersion of the present invention.

Next, the following paint was produced using this dispersion.

The following were added to the cans to form a grind mixture: 60 g of the fibrid dispersion described above, 15.6 g of propylene glycol, Tamol.
7.12 g of 731A, 0.56 g of KTTP, 0.68 g of Triton N-57, 0.68 g of TERGITOL NP-9, and 69.6 of titanium dioxide
4 g, 26.0 g of OPTIWHITE clay, and 26.0 g of SNOWFLAKE clay. This mixture was mixed with a Ross mixer at the maximum mixer speed for 5 minutes. Next, the Ross mixer was stopped, and a further 84.64 g of fibrid dispersion was added. The Ross mixer was restarted and operated at maximum mixer speed for 15 minutes. The resulting mixture was mixed with the following components (let down (let
down) compound: ROVACE 910
0, 102,8 g of acrylic resin, 4.6 g of DOWNOL DPnB
6.6 g of ACRYSOL RMB25 and 0.08 g of 28% by weight ammonia. The new mixture was mixed at 3000 rpm for 10 minutes to complete the manufacture of the paint.

The paint was tested and is reported in Table 2. The control paint was mixed in the same manner using only the components shown in Table 1.

Table 1 shows the control paint, ie the paint without fibrids, sample A, ie 0.15%
Figure 3 shows the formulation of a control with fibrids added directly to the paint grind, and Sample B, a control with 0.15% fibrids added from the fibrid dispersion of the present invention. For sample A, fibrids were added directly to the component mixture in the grind. That is, in Sample A, no fibrid dispersion was used. Table 1 Controls Sample A Sample B Fibrids-Used Used Fibrid dispersion--Used components (weight basis) F20W 0 0.15 0.15 Tamol 731A 0.55 0.55 0.55 KTTP 0.09 0.090 .09 Surfinol DF 0.56-Targinol NP-9 0.18 0.18 0.18 Triton N-57 0.18 0.18 0.18 TI-Pure (PURE) 18.20 18.20 18. 20 Optiwhite 6.80 6.80 6.80 Snowflake 6.80 6.80 6.80 Loves 9100 26.80 26.80 26.80 Daunol DPnB 1.20 1.20 1.20 Acrysol RM-825 1. 73 1.73 1.73 water 32.81 32.81 32.81 propylene glycol 4.10 4 .10 4.10 Colloid 643-0.5 0.5 A-1100-0.5 0.5 Aromax DM-16-0.5 0.5 Minugel PC-1.7 1.7 Table 2 shows these formulations. 3 shows the test results of the product. Table 2 Comparative Tests of Improved Formulations and Controls Controls Sample A Sample B Physical Properties Appearance White Milk White Milk White Milk-like Emulsion Emulsion-like Emulsion Texture 5.5 5 Gloss 00 00 Dispersibility 6 (m) 5 (m) 3 (s) Viscosity (cps) 2800 8300 2300 Deflection index 275 300 225 Relative viscosity (ratio visc.) Deflection index 10.0 27.6 10.2 Leveling 0 0 4 Tension ( PSI) 448 564 483 Elongation (%) 58 63 200 Adhesion 5 2 3.5 (0 (best) -5 (worst))

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] October 11, 1999 (1999.10.11)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

3. The method of claim 1, wherein the surfactant is non-ionic or anionic.
A dispersion as described.

4. The dispersion of claim 1, wherein the filler is selected from the group consisting of clay, calcium carbonate, talc, silica, titanium dioxide, mica, silicate, glass, oxide.

5. A silane, wherein at most 0.5% by weight of fibrids, at most 5% by weight of inorganic particulate filler are each present in a concentration sufficient to maintain the fibrids and inorganic filler in the dispersion . coupling agent is selected from the group consisting of titanates and zirconates, and together with a surfactant, an aqueous dispersion comprising comprising that it is incorporated in the resin composition, provided that the concentration in the resin composition of the aqueous dispersion There Ru concentration der to about 0.25% at most fibrid concentration of the resin composition, improved resin composition containing dispersed resin and additives.

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Claims (6)

[Claims] 1. A composition comprising at most 0.5% by weight of fibrids, at most 5% by weight of an inorganic particulate filler and a coupling agent and a surfactant, provided that the coupling agent and the surfactant are fibrid and An aqueous dispersion, wherein the inorganic filler is present in a concentration sufficient to maintain the dispersion. 2. The dispersion of claim 1 wherein the concentration of fibrids is at most about 0.4% and the concentration of inorganic particulates is about 2-4%. 3. The dispersion of claim 1, wherein the coupling agent is selected from the group consisting of silane, titanate, zirconate. 4. The method of claim 1, wherein the surfactant is non-ionic or anionic.
A dispersion as described. 5. The dispersion of claim 1, wherein the filler is selected from the group consisting of clay, calcium carbonate, talc, silica, titanium dioxide, mica, silicate, glass, oxide. 6. A coupling wherein at most 0.5% by weight of fibrids, at most 5% by weight of inorganic particulate filler are each present in a concentration sufficient to maintain the fibrids and inorganic filler in the dispersion. Mixing the aqueous dispersion comprising the agent with the surfactant together with the surfactant into the composition, provided that the concentration of the aqueous dispersion in the resin composition increases the fibrid concentration in the resin composition by at most about 0.1%. 25% concentration.
An improved resin composition comprising water or one having affinity for water, comprising a dispersed resin and additives.